Dyeing of polyolefin fibers in fast colours



United States Patent 3,235,322 DYEING 0F POLYOLEFIN FIBERS IN FASTCOLOURS Ryukichi Tanaka, Kazuhiro Teramura, Seichiro Yokoyama, and KeizoMiyamoto, Kyoto, and Shinpei Itoh,

Tokyo, Japan, assignors to Nitto Boseki Co., Ltd., Fukushima-shi, Japan,a corporation of Japan No Drawing. Filed July 30, 1963, Ser. No. 298,561

Claims priority, application Japan, Aug. 10, 1962, 37/331,066; Nov. 20,1962, 37/ 50,900 3 Claims. (Cl. 8-39) This invention relates to aprocess for the dyeing of polyolefin fibers. More particularly itrelates to a process for the dyeing of. polyolefin fibers by employing aspecific anthraquinone dye.

Hydrophobic property of fibers made of polyolefin like polyethylene andpolypropylene is due to their molecular structure of high regularity andtheir paraffinic nature. Consequently it is necessary to introduce notonly al iphatic higher alkyl radical but also paraffinic nature intostructure of a dyestuff molecule to obtain the dyestuff having enhancedaffinity to hydrophobic high polymers.

With an intention of finding characteristic dyestuffs suitable topolyolefin we have been working on synthesis of various kind ofanthraquinone dye and investigating the effect of structure on theaffinity of dye. As the result, dyestuffs expressed by followingchemical structures (C.I. Disperse Blue 23 and Blue 3) W ITTHCHzCHaOH(I? NHClEfzCHzOH l NHCHzCHaOH O I IHGH3 O N11 O NHg ll I II I I! I ll 0OH 0 NHz affinity to polyolefin is found to be poor on account of theinfluence of primary amine group contained in their molecules. AlsoN-substituent of anthraquinone like compounds expressed as followsNH-CHa l mb-CH3 has still poor dyeing affinity to polyolefin.

These facts show that increase of hydrophobic property of dyestuff alonedoes not improve dyeing affinity to polyolefin. Accordingly we must payattention to the fact that polyolefins have characteristic properties ofbeing hydrophobic due to hydrocarbon polymer and of having no functionalgroup to bind with dyestuff. From these points following methods can beconceived.

1) Enhancement of aflinity to polyolefinshaving parafiinic property byimparting paraflinic property to dyestuff itself by introducing alkylgroup.

(2) Enhancement of affinity to polyolefin by introducing a specificradical which has special selectivity to polyolefin.

We pointed out one time on the report of Journal of.

Textile Society of Japan, No. 18, vol. 6 [1962], that Japanese patentpublication No. Sho. 36/2 1,235 that dyestuffs having relatively largeparaflinic property, e.g.,

those as shown by following general formula have excel-1 lent dyeingproperty to polypropylene fiber from the standpoint of (1) 6 law (R isalkyl radical of more than 4 carbon atoms.)

This type of dyestuffs shows excellent dyeing affinity to polyolefin,but they cannot be called commercially perfect dyestuffs because thefastness of dyed substance is not satisfactory. Especially, poor lightfastness and the fastness to dry cleaning are serious disadvantages.

We changed our attention to the method (2) in searching for substitutionradicals which exhibit effective dyeing affinity to polyolefin, amongvarious anthraquinone derivatives, and found that following dyestuffsshow excellent dyeing affinity and fastness.

The dyestuffs useful in our method are those anthraquinone dyescontaining in at least one of the alpha positions, at least onehydroxyphenylamino radical The anthraquinone neucleus may contain otheratoms or radicals like halogen, alkyl, -OH, NH NHR This is the proof ofsimultaneous effect of above-mentioned two methods.

We have further found in our basic study that aniline is not adsobredbut alkyl aniline like can be adsorbed as the length of alkyl radicalchain increases and hydrophobic and paraffinic properties are increased.We applied this tendency to anthraquinone dye, as follows. Methylanthraquinone, methyl amino anthraquinone or their derivatives likethose shown by following formula IIIH; 0

III

II I I (wherein X=H, OH, NH NHCH etc.) cannot be adsorbed onpolypropylene fiber, but even in these compounds if hydrophobic andparaffinic properties are enhanced by introducing alkyl radical havingsuitable numbers of carbon atoms in the beta position of anthraquinonenucleus they show good affinity to fiber and can be adsorbed. Thiseffect is especially great when the number of carbon atoms in alkylradical is large.

Further we have made research about the effect of substitution radicalsin alpha position of beta alkyl anthraquinone upon dyeing afiinity andfound that we can dye polyolefin like polypropylene into fast colour bymaking them contain hydroxyphenyl amino radical blIHCHs Dyestuffsapplicable to the method of this invention belong tobeta-alkylanthraquinone as expressed by following general formula whichhave large paraffinic property and contain at least one hydroxyphenylamino radical in alpha-position.

(R is alkyl radical containing more than 3 carbon atoms). In theanthraquinone nucleus and/ or phenyl nucleus may contain substitutionatom or radical like hydroxyamino, alkylamino, arylamino alkylarylamino,aralkylamino, cycloalkylamino, halogen or alkyl.

By employing dyestuffs we have invented, it is possible to dyehydrophobic high polymer at a temperature of from room temperature to100 C. or higher than 100 C. It is also possible to employ swellingagent like carrier or other dyeing assistant.

In case of polyolefin fiber it is preferable to effect dyeing in aqueousmedium in which a dyestuff is emulsified and dispersed by a suitablesurfactant. Any temperature from room temperature to 100 C. givessatisfactory results. If dyeing assistant like suitable carrier issimultaneously used, or if high temperature is applied in case ofrelatively heat resisting polymer like polypropylene, better dyeingeffect is attainable. Application of thermosol method at suitablecondition affords also good result. Constitutional formulas ofantbraquinone dyes related to our invention are shown as follows:

| I Blue I o NH-CH;

o NHOH I I Blue I I o NH-(OHz)a-CH;

I I Blue I I am NH-CHzO II I O NII(CH2) CH3 Blue O NH i) I IH-(CH 5-CH3Reddish blue I I O NHCH2CHC4H9 2115 Blue II I I O NH(CHZ)1 CI'I3 E1110 0H -Q I I II I O NH(CH2) 17-6113 RcddlSh lJlllQ Violet H N A v m BlueBlue

Blue

Violet Blue Violet Blue Violet Reddish blue I NH-CH:CH1CH2C1 0211 NHCHzCHzN NH- -OH C Ho Blue

Blue

Blue

Blue

Reddish blue NH-CHs Following examples to show the embodiment of thisinvention.

Example 1 i I I G IIS 100 g. of polypropylene fiber is immersed in a dyebath made by dispersing 5 g. of the dyestufi having above formula and 5g. of trichlorobenzene in 3 l. of an aqueous solution containing 6 g. ofN-stearoyl-N-methyltaurine so as to become emulsion. The dyeing iscarried out at a temperature of from 90 C. to 100 C. for 1.5 hours. Thefiber is then Washed by Washing solution containing 5 g./l. ofN-stearoyl-N-methyltaurine with fiber to solution ratio of 1:30 at atemperature of from to for 30 minutes. After hot water Washing followedby cold water washing, a blue colour is obtained.

Example 2 g. of polypropylene fiber is immersed in a dye bath made bydispersing 5 g. of the dyestufl having above formula in 3 l. of anaqueous solution containing 6 g. of N-stearoyl-N-methyltaurine so as tobecome emulsion. The dyeing is carried out at a temperature of C. for1.5 hours in a tightly closed vessel. By proceeding as II o NH-Q-CsHn100 g. of polypropylene fiber is immersed in a dye bath made bydispersing 5 g. of the dyestulf having above formula in 5 l. of aqueoussolution containing 10 g. of N-stearoyl-N-methyltaurine so as to becomeemulsion. The dyeing is carried out in a tightly closed vessel at atemperature of C. for 1 hour. By proceeding as described in Example 1 agreenish blue colour is obtained.

Example 4 100 g. of polypropylene fiber is immersed in a dye bath madeby dispersing 5 g. of the dyestuff having above formula and 5 g. ofdiethylaniline in 3 l. of aqueous solution containing 6 g. ofN-stearoyl-N-methyl taurine so as to become emulsion. The dyeing iscarried out at a temperature of from 95 C. to 100 C.

for 1.5 hours. By proceeding as described in Example 1 a greenish bluecolour is obtained.

Example 5 l O NH 0121125 100 g. of polypropylene fiber is immersed in adye bath made by dispersing 10 g. of the dyestuffhaving above formula in3 l. of an aqueous solution containing 6 g. of N-stearoyl-N-methyltaurine so as to become emulsion. The dyeing is carried out at atemperature of from 90 C. to 100 C. for 2 hours. By proceeding asdescribed in Example 1, a blue colour is obtained.

Example 6 a? I II I OH O NH OH 100 g. of polypropylene fiber is immersedin a dye hath made by dispersing 5 g. of the dyestutf having aboveformula in 3 l. of an aqueous solution containing 10 g. ofN-stearoyl-N-methyl taurine so as to become emulsion. The dyeing iscarried out under pressure at a temperature of 120 C. for 2 hours. Byproceeding as described in Example 1, a violet colour is obtained.

Example 7 H II 0 0 5 g. of the dyestuff having above formula and 5 g. oftrichlorobenzene is dispersed to emulsion in 3 l. of aqueous solution ofdispersing agent containing 6 g. of N-stearoyl-N-methyl taurine. Intothis dyeing bath, 100 g. of polypropylene fiber is introduced and thedyeing is carried out at a temperature of from 90 C. to 100 C. for 1.5hours. By proceeding as described in Example 1, a red colour isobtained.

Example 8 S g. of the dyestuff having above formula and is dispersed toemulsion in 3 l. of an aqueous solution of dispersing agent containing 6g. of N-stearoyl-N-methyl taurine. Into this dyeing bath, 100 g. ofpolypropylene fiber is introduced and the dyeing is carried out in atightly closed vessel at a temperature of 120 C. for 1.5 hours. Bywashing as described in Example 1, a bordeaux colour is obtained.

1 2 Example 9 0 M3 H l K I can on:

| O OH 5 g. of the dyestutf having above formula and 5 g. of diethylaniline are dispersedto emulsion in 3 l. of an aqueous solution ofdispersing agent containing 6 g. of N-stearoyl-N-methyl taurine. Intothis dyeing bath, 100 g. of polypropylenefiber is introduced and thedyeing is carried out at a temperature of from C. to C. for 1.5 hours.By Washing as described in Example 1, a blue colour is obtained.

Example 11 I I C4119 H O NHC5H13 10 g. of the dyestufi having aboveformula is dispersed to emulsion in 3 l. of an aqueous solution ofdispersing agent containing 10 g. of N-stearoyl-N-methyl taurine. Intothis dyeing bath 100 g. of polypropylene fiber is introduced and thedyeing is carried out at a temperature of from 90 C. to 100 C. for 2hours. By washing as described in Example 1, a blue colour is obtained.

Example 12 l l O NH 041%;

5 g. of the dyestutf having above formula is dispersed in 5 l. of anaqueous solution containing 10 g. of N-stearoyl-N-methyl taurine. Intothis dyeing bath, 100 g. of polypropylene fiber is introduced and thedyeing is carried out under pressure at a temperature of C. for 2 hours.By washing as described in Example 1, a green colour is obtained.

Example 13 I E OH NH- OH 0.15 g. of the dyestufr' having above formulais dispersed in 100 cc. of aqueous solution containing 0.2 g. ofdispersing agent having formula of Into this dyeing bath 3 g. ofpolypropylene fiber is introduced and the dyeing is carried out at atemperature of from 90 C. to 100 C. for 1 hour. After dyeing the fiberis soaped at a temperature of from 70 C. to 80 C. and then Washed bywater. Mordant dyeing is carried out as follows:

(a) Dyed fiber is padded in aqueous solution of from 2 to 5 percentNi(SCN) and picked up so as to be from 80 to 100 percent by weight offiber. After dried in air, it is steamed at a pressure of from tolbs/in. for minutes. Further it is washed by water at a temperature offrom 60 C. to 80 C. and dried.

(b) Dyed fiber is introduced in 100 cc. of bath containing 0.2 g. ofpotassium bichromate and 0.2 g. of formic acid and treated at atemperature of from 90 C. to 100 C. for 1.5 hours.

(c) 0.3 g. of cuprous acetate is dissolved in 100 cc. of water. Intothis solution, dyed fiber is introduced and treated at 125 C. for lhour.

Example 14 (a) 0.3 g. of aluminum stearate is dispersed in a solutioncontaining 0.3 g. of dispersing agent having formula ca -Q0 0H2- CHzO)20H Into this solution 3 g. of propylene fiber is introduced and treatedat 125 C. for 1 hour. Soaping is lightly performed at a temperature ofabout 60 C.

(b) 0.5 g. of trichlorobenzene is emulsified in 100 cc. of watercontaining 0.2 g. of N-stearoyl-N-methyl tau 1 1- rine. Into thissolution, 0.15 g. of potassium bichromate and 0.15 g. of formic acid isintroduced. The fiber is treated at a temperature of from C. to C. for

1.5 hours, followed by soaping.

(a) Polypropylene fiber which is subjected to treatment (a) and (b) isintroduced into 100 cc. of water containing 0.2 g. of dispersing agenthaving formula of and 0.15 g. of dyestuff having Formula A in Example 13and treated at a temperature of from 90 C. to 100 C. for 1 hour.

(b') Treatment according to (a) is carried out at C. Among dyestuffsshown from No. 1 to N0. 48, the one which is effective formordant-dyeing by metal are as follows: No. 19, No. 28, No. 33, No. 34,No. 35, No. 42, No. 47, No. 48.

What is claimed is:

1. A method for dyeing polyolefin fiber which comprises treating thesame with a hydrophobic anthraquinone dye containing ahydroxyphenylamino radical in alpha position and an alkyl radical havingmore than three carbon atoms in beta position on the anthraquinonenucleus.

2. A method according to claim 1 in which the polyolefin ispolyethylene.

3. A method according to claim 1 wherein the polyolefin ispolypropylene.

References Cited by the Examiner UNITED STATES PATENTS 1,868,202 7/1932Grossmann 260-380 2,258,551 10/1941 Grossman 260-380 2,487,045 11/1949Dickey et a1 260378 X 2,605,269 7/1952 Bauxbaum 260-378 X 3,097,044 7/1963 Skeuse 8-55 FOREIGN PATENTS 645,540 7/ 1962 Canada.

809,495 2/ 1959 Great Britain.

838,687 6/1960 Great Britain.

NORMAN G. TORCHIN, Primary Examiner.

J. HERBERT, Assistant Examiner.

1. A METHOD OF DYEING POLYOLEFIN FIBER WHICH COMPRISES TREATING THE SAMEWITH A HYDROPHOBIC ANTHRAQUINONE DYE CONTAINING A HYDROXYPHENYLAMINORADICAL IN ALPHA POSITION AND AN ALKYL RADICAL HAVING MORE THAN THREECARBON ATOMS IN BETA POSITION ON THE ANTHRAQUINONE NUCLEUS.